| 成丽君,廖骞.NNN型配体及其钨卡宾配合物合成[J].,2022,62(2):111-116 |
| NNN型配体及其钨卡宾配合物合成 |
| Synthesis of NNN-type ligand and its tungsten carbene complex |
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| DOI：10.7511/dllgxb202202001 |
| 中文关键词: 钨卡宾配合物 钳形配体 三苯基氯甲烷 配位反应 |
| 英文关键词: tungsten carbene complex pincer ligand triphenylchloromethane coordination reaction |
| 基金项目:国家自然科学基金资助项目(21702024). |
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| 中文摘要: |
| 将4，4′-二甲基二苯胺依次经硝化和还原后，合成了双(4-甲基-2-氨基苯基)胺．此化合物与三苯基氯甲烷进行N 烷基化反应，高产率地得到了一种新的氨基-NNN钳形配体2，2′-二(三苯甲基氨基)-4，4′-二甲基二苯胺．该配体在空气中稳定，且能与(t-BuO)3W≡CPh反应形成一种新型的钨卡宾配合物．通过核磁共振、X-射线单晶衍射等方法对该卡宾配合物研究发现，配体的3个N原子并未全部参与配位，而是有1个N原子取代基上的苯环参与了配位．通过DFT计算，发现NNC型配合物比NNN型配合物能量更低． |
| 英文摘要: |
| Bis(4-methyl-2-aminophenyl)amine was synthesized by nitration and reduction of 4,4′-dimethyldiphenylamine. After N-alkylation of this compound with triphenylchloromethane, a new amino NNN-pincer ligand, 2,2′-bis(triphenylmethylamino)-4,4′-dimethyldiphenylamine was obtained in high yield. This ligand is stable in air and can coordinate with (t-BuO)3W≡CPh to form a new tungsten carbene complex. The NMR and X-ray single crystal diffraction show that not all the three N atoms of the ligand coordinate to the metal, but the benzene of one N atom′s substituent coordinates. DFT calculation proves that the energy of NNC-type complex is lower than the energy of NNN-type complex. |
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